Photographic emulsions and new coupling compounds



United States Patent 2,772,161 Patented Nov. 27, 1956 PHOTOGRAPHICEMULSIONS AND NEW COUPLING COMPOUNDS Anthony Loria and Edward T. Pesch,Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New Jersey N Drawing. Application October 14, 1954,Serial No. 462,364

11 Claims. (Cl. 96-55) This invention relates to new compounds andphotographic emulsions containing them.

The new compounds of our invention can be represented by the followinggeneral formula:

wherein R represents a hydrogen atom or an alkyl group, such as methyl,ethyl, etc., R1 represents a hydrogen atom, a methyl group, or an alkalimetal atom, such as sodium, potassium, etc., 11 represents a positiveinteger of from 1 to 2 and Z represents an aromatic nucleus (e. g.,benzene, naphthalene, etc.), said nucleus being substituted by a radicalselected from the group consisting of a pyrazolone radical, i. e., aradical of the formula:

wherein R2 represents an alkyl group, such as methyl, ethyl, n-propyl,etc., or an aromatic radical, such as phenyl, chlorinated phenyl,brominated phenyl, naphthyl, etc.; a phenolic radical, such ashydroxyphenyl, hydroxynaphthyl and substituted derivatives thereof; orthe radical of an open chain ketomethylene compound. The portion of themolecule represented by the above general formula wherein Z is definedis well known in the art of color photography. The portion of themolecule represented by Z is that portion of the compound of Formula Iwhich condenses with the oxidation products formed during development.Such principles areiwell understood by those skilled in the art ofphotography, and our invention is to be interpreted in the light ofthisparticular prior art. However, we have found the compounds representedby the following general formula, which compounds are embraced byFormula I above,are particularly useful for the purposes of ourinvention.

II. OCH2OOOOH3 651111 (tert.)

tuted thereon a pyrazolone radical as defined above un- 0 der Z, aphenolic radical, or a radical containing an open a. j

chain ketomethylene group.

Accordingly, it is an object of our invention to provide new compoundsuseful in color photography. Another object is to provide a method formaking such compounds. Still another object is to provide newintermediates which are useful in preparing couplers useful in colorphotography. Another object is to provide a method for making suchintermediates. Another object is to provide photographic emulsionscontaining the new compounds of our invention. Other objects will becomeapparent from a consideration of the following description and examples.

. The compounds represented by Formula 11 above are particularly usefulin preparing solutions for incorporation in photographic emulsionsinasmuch as the ester groups are easily hydrolyzed in alkaline solution(e. g., aqueous sodium hydroxide, aqueous potassium hydroxide, etc.) toproduce the alkali metal salts which are quite soluble in the solutionsto be added to the photographic emulsion. Also, in the event it isdesired to incorporate the new compounds of our invention inphotographic developing solutions, the compounds of Formula II areeasily incorporated in such developing solutions by simply adding thecompound to an aqueous alkaline solution as described above.Acidification of these alkaline solutions produces the free carboxylicacids, i. e., compounds of Formula I wherein R1 is a hydrogen atom.

The compounds of Formula II can advantageously be prepared by condensinga compound having the follow ing'formula;

III. (II) moo 0 o omo-Q-o-m wherein Z has the values given above. Thesecondensations are advantageously carried out in the presence of anacid-binding agent, such as alkali metal acetates, pyridine, etc.,although the use of such an acid-binding agent is not necessary. Thecondensations are advantageously carried out in the presence of an inertsolvent, such as anhydrous acetic acid, acetone, acetonitrile, xylene,diethyl ether, etc. Temperatures varying from room temperature to thereflux temperature of the reaction mixture can be employed, although wehave found that it is quite convenient to simply heat the reactionmixture on the steam bath for a short period of time.

The aminic coupling components represented by Formula IV above have beenpreviously described in the art of color photography, and as notedabove, our invention is to be construed in the light or" the prior art.For example, a very large number of such aminic coupling components havebeen previously described and it is not believed essential to enumeratethis large body of material herein, inasmuch as this particularembodimerit of the invention has been described in detail in a largenumber of S. patents. Typical aminic coupling components have beendescribed in one or more of the following patents:

Name U.S. Patent Date of Issue Salminen et a1 2, 423, 730 July 8, 194.7.Weissberger et al 2, 511, 231 June 13, 1950. Weissberger et a1--. 2,589,004 Mar. 11, 1952. Loria et a1 2, 600, 788 .Tune 17, 1952.Weissberger et a1 2, 618, 641 Nov. 18, 1952.

The following examples will serve to illustrate more fully the mannerwhereby we practice our invention.

a Example I .Z,4 bis( carbometh oxymethaxy bertzaldehyde' C H3 0 E llnoQ-oomomom 2NaBr 76.5 grams (0.5 mole) of methyl bromoacetate, 34.5grams (0.25 mole) of fl-resorcaldehyde, and 200 cc. of

7 dry methanol were placed in a dry 500 cc. 3-neck flask fitted with asealed stirrer and a condenser equipped with a calcium chloride dryingtube. The third neck of the flask was fitted with a dropping funnel (atype of threeneck flask also equipped with a condenser carrying acalcium chloride drying tube).

In the dropping funnel was placed 200 cc. of absolute methanol andtoit'was added (in 30 minutes) 11.5 g.

(0.5 mole) of clean sodium. When the sodium had reacted completely, themethoxide solution was added dropwise to the refluxing solution of thealdehyde and bromoester overa period of fivehours. 'The reaction mixturewas refluxed two hours longer, then allowed to stand over-night at roomtemperature. The crystalline solid which SeparatedJWaS filtered, washedwell with water and dried. This fraction weighed 40 grams, and melted at90-1 C.

The reaction filtrate was drowned in 1 liter of water.

The solid which formed after standing one hour was filtered, washed inwater, dried. This fraction weighed 13 grams, and also melted at 90-1 C.a

' Total yield was 53 grams or 71% of the theoretica 74.5 grams.

Example 2.2,4-l2is(carbornethoxymethoxy)- benzoic acid eonroolouiQ-oomoowu; KMnO 3 ?CHzCO2 CH3 OCH2CO:OH3

A solution of 55 g. of 2,4-bis-(carbomethoxyrnethoxy)- benzaldehyde in500 ml. of acetone was added dropwise to a solution of potassiumpermanganaterin 1 liter of water. The reaction mixture wasstirredvigorously at 4550 C. for four hours, and then sulfurdioxide gas waspassed into it. The white crystalline precipitate formed was filtered,washed well with cold water and crystallized from methanol. 7

Analysis.-C1aH14Oa:

Gale. Found Example 3.Dimethyl-4-chloroformyl-I,3-

phenylene bis(0xyacetate) 7 o ornoozom so 012 ?CH2C 02GB; Q4 on, 00205 Amixture of 7.45 g. of 2,4-bis(carbomethoxymethoXy)benzoic acid and 50ml. of thionyl chloride was shaken until complete solution had takenplace, and then allowed to stand overnight. The excess thionyl chloridewas removed under reduced pressure from a water bath at 30 C. untilconstant weight was reached and the solid residue was used withoutpurification.

In a manner sirnlar to that illustrated in Examples 1 to 3 above, otheracidchlorides suitable for'condensing with the compounds of Formula IVcan be prepared. For example, the methyl bromoactate of Example l can bereplaced by a molecularly equivalent amount of methyl,(i-bromopropionatqor methyl a-bromopropionate to givedimethyl-4-chloroformyl-1,3-phenylene "bis (}3- oxypropionate) anddimethyl-4-chloroformyl-1,3-phenyl bis(a-oxypropionate), respectively,by proceeding as outlined above in Examples 1 to 3.

, fiuxed for one hour in 150 ml. of dry acetone.

Dimethyl 4 chloroformyl-1,3-phenylene bis(oxyacetate) 9.4 g. (0.03 molem-nitroaniline 4.15 g. (0.03 mole) and dimethylaniline 3.6 g. (0.03mole) were re- The re action mixture was cooled to about 10 C. and theprecip itated product was filtered, slurried in 200 ml. of cold water,filtered again and dried in a hot cabinet. The dry material wascrystallized from dry ethylene glycol and a white crystalline powdermelting between 195 and 197 C. was obtained.

Example 5 .-'2,4-bis( carbom ethoxymethoxy)-3'- amino benzanilide GONH IH2 Q-oomo 020E: Go 01120 02011; a

' Goren A Parr hydrogenation bottle was charged with 7 g. of 2,4bis(carbomethoxymethoxy) -3'-nitrobenzanilide, ml. of absolute ethanol,0.5 g. of Raney nickel catalyst and 0.1 g. of sodium carbonate. Thebottle was shaken on a Parr hydrogenator for one hour under 38 pounds ofhydrogen pressure at room temperature. The theoretical volume ofhydrogen was taken up in a short'time" of shaking. The Catalyst wasfiltered out of the solution and The filtrate was cooled, theprecipitate that formed was filtered, washed first with a 3% sodiumacetate solution, then with water and dried. The dry product wascrystallized twice from acetonitrile and melted at 2089 C.

the filtrate was evaporated to about 50 ml. and left to stand. Thecrystalline precipitate that formed on standing was filtered, washedwith 25 ml. of cold absolute ethanol and dried. crystallized frompropanol, the product melted at 1078 C. Analysis:

Analysis.-C19H2oN2O7:

o H 01 N Cale. Found Calc. for omrrraohNgomuun- 62.8 5.8 8.6 3.1

o 58.7 59.0 10 Found 62.3 5.8 8.4 3.2 H- 5.2 5.1 N 7.2 7;;

The phenol component employed in the above example Example6.-5-(2,4-dicarbomethoxymethoxybenzamido)- 2 (2,4 ditertampylphenoxfibenzamido 2,4 dichlor0-3-methylphen0l A mixture of 5.44 g.(.01 mole) of 6-[S-amino-2- (2,4 di'- tert. amylphenoxy)benzamido] 2,4dichloro-B-methyIphenol and 3.06 g. (.01 mole) of2,4-di-carbomethoxymethoxybenzoyl chloride in 150 ml. of dryacetonitrile was refluxed for 30 minutes and filtered hot.

was prepared by condensing 4-amino-2,6-dichloro-mcresol (C. A. Vol. 35.page 3249) with 2-(2',4'7di-t-amylphenoxy)-5-nitrobenzoyl chloride,followed by reduction of the nitro group as described in U. S. Patent2,589,004 (Example 3).

Example 7.-1-phenyl-3-[2-(2,4-di t amylphenoxy) -5- (2,4dicarbom'ethoxymethoxybenzamido) benzamidol- S-pyrazolone Nee-N110 o@ -oorno more A slurry of 2.8 g. (.0043 mole) of 1-phenyl-3-[2-(2,4- Thiscompound was prepared by the same method dedi -.t amylphenoxy) 5aminobenzamido] 5 pyrascribed in Example 7. The crude product wasisolated zolone in 20 cc..ofdry xylene was mixed with a solution as agum, which was then recrystallized twice from be of 1.38 g.(.0045'mole') of 2,4-dicarbomethoxymethoxyzene yielding a light tansolid, M.'P. 146-8 C. benzoyl chloride in 15 cc. dry xylene. The mixturewas V refluxed for 2 /2 hours, complete solution occurring. TheAnalysis: xylene solution was filtered hot, and poured into 50 cc; ofligroin, a precipitate separating. The solid was filtered, washed withligroin, and recrystallized three times 7 7 V p M from benzene. Therewas obtained a white, crystalline 1Q E e ent V 0810- Found. solid, M. P.186-8 C. p

Analysts: 7 r I H 6.3 6.1

Cale. Foundg: gg, & The phenolic component used in the above example was6.95 7. 4 prepared as described in our copending application Serial Thepyrazolone component employed in the above ex- 2,721,798, issuedOctober25,"1955).

' Example 9. 1 (2,4,6-trichlor6phenyl)-3-[3-(2,4-dicfir Ibomethoxymethoxybenzamido benzamr'do] -5 pyra :l

zoldne 7 0001 NH: 01 OOHnCOsOH; /N=ONHOO p 01 N I t mmobrom N300 01 I/N=O -NHOO- OOHHOOEOH! OCH2 01 ll 0 v ample was prepared'as describedinthe copending ap- A slurry' of '.3.97"g.: .(.01' mole) of,1-(2,-4,6-trichloroplication Serial No 260,099, filed December 5, 1951,in 45 phcnyl)3 (3aminobenzamido)-5-pyrazolone.; in'20 cc. the names ofI. Salminen and A. Weissberger,'-now U. S. of ,dry xylene {was mixed,with a solution of ,3.1 g. (.01 Patent 2,694,718, issued November16,1954. mole) of 2,4-dicarbomethoxymethoxybenzoyl chloride in Example8.1-hydroxy-N-{4-[242,4-di-t-amylphenoxy)- 5 (2,4dicarbomethoxymethoxybenzamido) benzamid0JphenethyB-Z-naphthamide 0001OH NH, OOHnOOzOHa -o0NHoH,oH,--'-N11oo p W .oorno 0,057.

OOHzOOzOHs on NHGO OOHaOOzOH! OONHOHQOHQ-NHQOQ OIHII No. 378,158, filedSeptember 2, 1953 (now U. S. Patent,

9 20 cc. dry xylene. The mixture was refluxed with stirring for twohours. Complete solution did not occur. The mixture was cooled, and theprecipitate was filtered. The solid was pressed dry on the filter, andrecrystallized from a large volume of acetonitrile. A white powderysolid was obtained, M. P. 210-3 C.

The pyrazolone component used in the above example has been previouslydescribed in U. S. Patent 2,618,641.

Example 10.a (4-meth0xybenzoyl)-4-{3-[2,4-bis(carbomethoxymethoxy)benzamido] phenylcarbamylmeth oxy}acetanilide (IJOH2COIOHa Q CHsCOaCHSmmoooomoo-Q-ou CONE NEG OOHzOQNH:

OOHaO 020 OOIIIH alkali, antifoggants, etc. When the exposed emulsionsare developed with the color developing agents in the presence of thecouplers containing the pyrazolone group, magenta dye images areobtained, those couplers having phenolic hydroxyl groups such as anaphthol group give cyan dye images and those containing the open chainreactive methylene group yield yellow dye images.

When incorporating the couplers into emulsions, the ester groups of thecoupler are preferably hydrolyzed by treatment with alkali in alcoholsolution by the method of the Salminen et a1. U. S. patent applicationSerial No. 774,890, published April 24, 1947 and now abandoned. Thehydrolyzed coupler compound now containing both free carboxyl groups isthen incorporated into the emulsion in the required quantity. Thecouplers may be used in emulsion layers containing gelatin or otherwater permeable colloid carriers such as albumin, collodion, organicNaOAc Xylene NH0 0 omoQamoo 0111c o-Qo on;

Ethyl-m-(p-methoxybenzoyl)acetate 0.46 g. (.0025 mole), 1.1 g. (.0025mole) of 2,4-bis(carbomethoxymethoxy) -3' [a (4" aminophenoxy)acetamido]benzanilide and 0.1 g. of sodium acetate were refluxed in ml. of dryxylene for one hour. During the heating a white solid had come out ofsolution. The mixture was cooled, the solid filtered, and washed firstwith petroleum ether several times and then with water and dried. Thedry product was crystallized from a large volume of acetonitrile andshowed a M. P. of 1846 C.

Cale. Found C- 62. H 4. N 5.

esters of cellulose or synthetic resins. The emulsion may be supportedby transparent medium such as glass, a cellulose ester or syntheticresin or nontransparent medium such as paper or an opaque celluloseester. The emul sion may be coated as a single layer or as superimposedlayers on one or other sides of the support. The emulsion layers of amultilayer color film containing the couplers of the invention may bediiferently sensitized and may be sensitized either in the natural orfalse orders.

A typical color developer for use in developing emulsion layerscontaining the coupler compounds of the invention is as follows:

Grams Z-amino-S-diethylaminotoluene sulfate 2.5 Sodium sulfite(anhydrous) 5 Sodium carbonate (anhydrous) 20 Potassium bromide 2 Waterto 1000 cc.

While the coupler compounds of the invention are primarily intended foruse in emulsion layers, they can be used in color developingcompositions such as given above. The couplers are incorporated into thedeveloper compositions by first dissolving in a solvent such asisopropyl alcohol and this solution is then added to the alkalinedeveloper composition. About three grams of coupler are suitable for usein developer compositions such as the above.

1 1 Other useful developers comprise the hydrochloride or sulfate ofdiethyl-p-phenylenediamine, N-methyl-p-phenylenediamine, p-aminophenol,dimethyl p phenylenediamine, etc. r

We have also found that acidic-type couplers can be 5 condensed withcompounds of the type:

V. f z.

( uv-000R! wherein R1 has the values given above and R represents analkylene group, e. g.,,methylene, ethylene, etc. The preparation ofthese couplers can be diagrammed as follows, for example:

OH OH Q-on 061150001 Such couplers are, in general, not nearly so usefulas those represented by Formulas I and H above, however. A somewhatsimilar coupler which we have prepared is:

-o o 0 Cells Iii O (])CH(GH2)"-1COOR1.. "1.1;

HNO:

HOAO

wherein R represents a member selected from the group consisting of ahydrogen atom and an alkyl group,R1

represents a member selected from the group consisting- When thecompounds of Formula I or 11 above whereinRr is a methyl group areincorporated in an aqueous photographic emulsion, spontaneous hydrolysisensues, resulting in the formation of compounds wherein R1 is hydrogenoralkali metal, depending on the pH 'of the emulsion H a V What we claimas our invention and 'desire secured by Letters Patent of the UnitedStates is:

1. A photographic silver halide emulsion'containing a compound selectedfrom those represented by the follow! 7 ing' general formula: a

r r ocHwrmn-roooal maroomomomoQ-oamfl) of a hydrogen atom, a methylgroup,-and an alkali metal atom, 12 represents a'positive integer offrom 1 to 2,

"and Z represents a mononuclear aromatic radical having substitutedthereon a radical containing apyrazolone radical represented by thefollowing general formula;

I3 14 compound selected from those represented by the followcompoundselected from those represented by the foling general formula: lowinggeneral formula: t

Z1 OCHaCOOR1 Z1 H1000R1 u 5 i NH .C.. .0CH2OOOR1 7 NH-O -0OH1OOOR1 o o Ionrueert. 10 osnuo l O H11(tert.) C5H1r(tert.)

wherein R1 represents an alkali metal atom and 1 wherein R1 representsan alkali metal atom and Z1 reprel'epfesellts an Omatic radicalSubstituted y a radical sents an aromatic radical containing a phenolicradical. containing a pyrazolone radical selected from those repre- 6. Aphotographic silver halide emulsion containing a sented by the followinggeneral formula: compound selected from those represented by thefollowing formula:

N=o m-N l o oH1o 0 0 R1 c-oH on NHCO o 01 NHoo 00111000111 wherein R2represents a member selected from the group consisting of an alkyl groupand an aromatic group; OH; 0 a phenolic radical and a radical containingan open chain I I ketomethylene group. 01 O1H11(tert.)

4. A photographic silver halide emulsion containing a compound selectedfrom those represented by the following general formula:

O HuQert.)

Z1 0 0 01120 O 0 R1 p wherein R1 represents an alkali metal atom. vOOHflOOORI 7. A photographic silver halide emulsion containing a 40compound selected from "those represented by the following formula:

Osmium) OOH 000R l NHOO OsHnfiiert.)

N=G-NHCO OCH2COOR1 I 0 C 2 l wherein R1 represents an alkali metal atomand Z represents an aromatic radical containing a radical represented bythe following general formula:

O C H11(tert.)

/N=O Rr-N\ I 0Ha 051111 (tert. 0 wherein R1 represents an alkali metalatom.

8. A photographic silver halide emulsion containing a wherein R2represents a member selected from the group compound selected from thoserepresented by the folconsisting of an alkyl group and an aromaticgroup. lowing formula:

ooH1cooR1 on NHOO 00H1000R1 oonnomom-Q-rrnoo-Q OsHultmt.)

sHuflielt.)

5. A photographic silver halide emulsion containing a wherein R1represents an alkali metal atom.

15 l6 9. A photographic silver halide emulsion containing :1 wherein Rrepresents a member selected from the group compound selected from thoserepresented by the folconsisting of a hydrogen atom and an alkyl'group,R1

lowing formula: represents a member selected from the group consistingwherein R1 represents an alkali metal atom. V of a hydrogen atom, amethyl group, and an alkali metal 10. A photographic silver halideemulsion containing atom, 11 represents a positive integer of from 1 to2, and

a compound selected from those represented by the fol- :15 Z representsan aromatic radical having substituted therelowing formula: V

r) omo'oom o omo 0 0 R1 OOITIH wherein R1 represents analakli metalatom. V on a .radicalwhich couples with the oxidation product of 11. Aprocess of color development comprising .de- 30 said @01 1 p?- vclopingan exposed photographic silver halide emulsion in the presence of acolor developer and a compound v References citefl in h file of thisPatent selected from those represented by the following general fUNI'IEDSTATES PATENTS formulai 35 2,389,575 Kirby et al." Nov. 20, 1945R i V 7 2,622,086 Ledrut Dec. "16, 1952' I r 2,640,056 Kendall et a1.May 26, 1953 O OCHWHQH-PCOOM 7 p 2,657,134 Graham et a1. Oct. 27, 1953'.Z -NH G I -0. 3n(o-H,),.-1 oo0R1 V e

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A COMPOUND SELECTEDFROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA; WHEREIN RREPRESENTS A MEMBER SELECTED FROM TH GROUP CONSISTING OF A HYDROGEN ATOMAND AN ALKYL GROUP, R1 REPRESENTS A MEMBER SELECTED FROM THE GROUPCONSISTING OF A HYDROGEN ATOM, A METHYL GROUP, AND AN ALKALI METAL ATOM,N REPRESENTS A POSITIVE INTEGER OF FROM 1 TO 2, AND Z REPRESENTS ANAROMATIC RADICAL HAVING SUBSTITUTED THEREON A RADICAL WHICH COUPLES WITHTHE OXIDATION PRODUCT FORMED DURING COLOR DEVELOPMENT.